Silver halide emulsions stabilized with compounds having a single aziridine group in the molecule



SILVER HALIDE EMULSIONS STABILIZED WI'I'H COMPOUNDS HAVING A SINGLE AZIRIDINE GROUP IN'THE MOLECULE Filed April 12. 1965 Dec. 16. 1969 ummmo 5H o ETAL 3,484,242

oeusmrw) INvENToRs Fun/mm msma NOBUO mmnoro MITsuNoRI suarvnnn uuu HfiYfiSHI and In United States Patent Int. Cl. misc 1/34 US. Cl. 96-109 Claims ABSTRACT OF THE DISCLOSURE A compound having a single aziridine group in the molecule is used as an antifoggant in a silver halide photographic material, the aziridine group being wherein R R and R are each hydrogen, a methyl group or an ethyl group.

The present invention relates to a silver halide photographic material containing a fogging inhibitor and a stabilizer.

It has been well known that the photographic sensitivity of a silver halide photographic emulsion can be very effectively increased by the addition of natural active gelatin, a compound containing unstable sulfur, a noble metal salt, a polyalkylene oxide derivative, and the like. However, since fogging tends to be increased by the addition of such materials, the addition of a fogging inhibitor is necessary to suppress the increase of fogging.

Many fogging inhibitors were reported for suppressing such fogging but though the addition of these compounds decreases fogging of a photographic material, it reduces the sensitivity of the photographic material.

Therefore, an object of this invention is to provide a fogging inhibitor for a silver halide photographic material that does not reduce the sensitivity of the photographic material.

Another object of this invention is to provide a silver halide photographic emulsion the fogging of which is suppressed Without reducing its sensitivity.

A further object of this invention is to provide a process for suppressing the formation of fog in a photographic material when it is preserved under severe conditions of high temperature and high humidity.

An additional object of this invention is to provide a photographic emulsion, the sensitivity and the contrast of which are scarcely afiected by aging.

A still further object of this invention is to provide a process for suppressing the formation of fog without decreasing the sensitivtiy of a photographic material in cases Where a gelatin coating of the photographic material is preliminary hardened with formalin, etc., prior to its development.

These objects can be attained in the present invention by the addition of a compound having a single aziridine group. Typical examples of compounds having a single aziridine group in the molecule are shown below.

An example of such compounds is a compound shown by the following general formula t /CR2 YXN CH-Ra wherein X represents -CO, CS-, or 402- Y represents an alkyl group, an aryl group, or

(where R, and R each represents hydrogen, an alkyl group, a cyclic alkyl group, an aryl group, or an aralkyl group); and R R and R each represents a hydrogen atom, a methyl group, or an ethyl group.

Specific examples of compounds shown by the abovementioned formula are and CH2 A further type of antifoggant compound used in this invention is one shown by the general formula Other types of the compound used as an antifoggant in this invention is a compound shown by the general (III) wherein R R and R each represents a hydrogen atom, a methyl group, or an ethyl group and Z and Z each represents NH NH.R

wherein A represents H, C -C alkyl, COOR (wherein R is an alkyl group, an aryl group, or an aralkyl group),

-CN, CONH OCHC or an aryl group; R R 1 and R each represents a hydrogen atom, a methyl group, 4

or an eth l rou R re resents a h dro en atom, a

methyl g or f g (wharg Ragis an alkyl or O-R (where R; and R each represents a hydrogen group); and m and n each represents 0 or 1' atom, an alkyl group, a cyclic alkyl group, an aryl group,

Specific examples of the compound shown by Foror a.mlky1grup)' mula II are IHSgfegrfic examples of compounds shown by Formula m H C C N J m C m 0 4 H H C C m w H 4 OHJU m H C m m n C C C n c N c C o N W 3 N n\ /H C C m .0 O 4 5 m H C C N m a o H H i 4 w O w m W m N C m m m a C 2 H H C C C m 2 CIN 2 N z N 4 O 0 7 2 3 m 2 wi w w u H m H i J OHJV JUNO OHJV W 4 5 5 H H 4 d e o w w The above-illustrated compounds each having one aziridine group in the molecule may be prepared by the addition reaction of an isocyanate or an active vinyl compound with ethyleneimine or an alkyl ethyleneimine (cf., Annalen der Chemie; vol. 556, page 210) or the substitution reaction of an active halogen compound with ethyleneimine or an alkyl ethyleneimine (cf., Berichte der Chemie; vol. 32, page 2037 and J. of American Chemical Society; vol. 77, page 5918).

The compounds used in this invention each having one aziridine group (wherein R R and R each represents a hydrogen atom, an ethyl group or a methyl group) in the molecule may be used alone or as a mixture thereof. Further, they may be used with other stabilizers.

The fogging inhibitor of this invention may be added in an emulsion at any time before the emulsion is applied on the support, but it preferably added at a time between after-ripening and coating. There is no limit on the amount of the compound, but a suitable amount is 0.1400 g. per mole of AgX (where X represents a halogen atom) in the silver halide photographic emulsion.

In the above explanation, the fogging inhibitor of this invention is described as being added to a silver halide photographic emulsion, but the invention. is not so limited, since the compound may also be added to a protective coating layer of the photographic material. In the latter case, a suitable amount of the compound is 0.5-500 g. per 1 kg. in gelatin of the protective coating layer.

The fogging inhibitor of this invention may suitably be incorporated in the photographic sensitive emulsion and/or protective coating in the form of a solution in a solvent having no bad effect on the silver halide photographic emulsion, such as water, a lower alcohol (e.g., methyl alcohol, ethyl alcohol, or isopropyl alcohol), or a ketone (e.g., acetone).

The fogging inhibitor of this invention can be incorporated into such photographic materials as, a negative emulsion for black and white photography, an X-ray emulsion, a coupler-in-emulsion type color photographic emulsion wherein a color coupler is incorporated in the emulsion, and a coupler-in-developer type color photographic emulsion wherein a color coupler is incorporated in a developer. However, the best results are obtained in the case a silver iodobromide gelatin emulsion.

The silver halide photgraphic emulsion may the sensitized chemically by a conventional method, such as, by the addition of a compound containing an unstable sulfur, e.g., ammonium thiosulfate or an aryl thiourea (cf. P. Glafkides Chimie Photographique 2 cm Edition, Publication Photocinema, Paul Montel Paris; page 297-299, 1957), by the addition of a gold compound, e.g. a complex salt of monovalent gold and thiocyanic acid (cf. ibid.; page 301), by the addition of a polyalkylene oxide derivative, or by a mixture thereof. Further, the silver halide photographic emulsion may be optically sensitized by the addition of an optical sensitizer such as a cyanine dye or a rnerocyanine dye (cf., Shinichi Kikuchi, Kagaku Shashin Binran (the 2nd Volume), page 13-24, 1959 published by Maruzen Co.).

The invention will be explained further by the following examples referring to the accompanying drawing showing the relation between exposure and density of color film (No. 1) that did not contain the fogging inhibitor of this invention and color film (No. 2 to No. 5) containing a fogging inhibitor of this invention.

EXAMPLE 1 by Tokyo Shibaura Electric Co.) and then developed for 8 minutes at 20 C. in a developer having the following composition:

N-methyl-p-aminophenol sulfate g 2 Sodium sulfite (anhydrous) g Hydroquinone g 5 Borax g 2 Water to liter 1 The photographic properties of the developed photographic film were determined and compared with those of a photographic film prepared and developed under the same conditions except that the fogging inhibitor of this invention was not used. The results were as follows:

As shown in the above results, the formation of fog was clearly suppressed by the fogging inhibitor of this invention.

7 EXAMPLE 2 N-methyl-p-aminophenol sulfate g 2 Sodium sulfite (anhydrous) g 80 Hydroquinone g 8 Sodium carbonate (anhydrous) g 40 Potassium bromide g 3 Water to liter 1 The photographic properties of the thus developed photographic film were compared with those of a photographic film treated under the same conditions except that the fogging inhibitor of this invention was not used. The results are shown below, which showed that the formation of fog was clearly suppressed by the addition of the fogging inhibitor of this invention.

Quantity (g./l. mol of Relative Name of compound AgX) sensitivity Fog None 100 0. 19 Compound 4 4. 1 97 0. 16 D 8. 2 94 0. 1] Compound 18 11.5 97 0. 13 D0 23. 0 92 0. 17

EXAMPLE 3 A sulfurand gold-sensitized gelatin-silver iodobromide reversal color emulsion, to which was added l-acetyl-Z- methyl-aziridine (Compound 12), methyl 3 (l-aziridinyl)-propionate (Compound 16), or 2 (1 aziridinyl)- 4,6-bis methoxy 1,3,5 triazine (Compound 28), was coated on a film base. The sensitive film was exposed on a sensitometer NSG Type-II, treated in a hardening bath having the following composition for 3 minutes at 27 C.

Sodium pyrophosphate g 20 Sodium sulfate g 50 37 formaldehyde ml 17 caustic soda ml 1 Water to liter 1 rinsed with water for 4 minutes at 27 C., and then developed for 7 minutes at 27 C. in a developer having the following composition:

The photographic properties of the thus developed photographic film were compared With those of a photographic film prepared and treated under the same conditions except that the fogging inhibitor of this invention was not added and the results were as follows. This showed that the formation of fog was effectively suppressed without reducing the sensitivity by the addition of the fogging inhibitor.

Quantity Com ound mol of Relative p g h AgX) sensitivity Fog 100 0. 85 5. 95 112 0. 52 11. 9 108 0. 31 7. 6 130 O. 36 0 15. 2 115 0. 24 Compound 28 5. 46 130 0. 32 D0 10. 92 120 0. 12

8 EXAMPLE 4 1 benzoyl aziridine (Compound 13) or 2 (l-aziridinyl)-4-anilino-6-phenoxy-1,3,5-triazine (Compound 34) was added to a 5% gelatin solution and 5 ml. of the solution was applied on a cabinet size dry plate (about 200 sq. cm.) that had been coated with a sulfurand goldsensitized gelatinsilver iodobromide emulsion for reversal color photographic material. The double-coated dry plate was exposed on a sensitometer NSG Type-II and then developed in a developer having the following composition for 7 minutes at 27 C.

N-methyl-p-aminophenol sulfate g 1 Sodium sulfite (anhydrous) g 60 Hydroquinone g 10 Potassium bromide g 5 Potassium thiocyanate g 1.5 0.1% potassium iodide ml 5 Caustic soda g 2 Water to liter 1 The photographic material of this example was compared with the same photographic material that did not include the fogging inhibitor of this invention but where all other conditions were the same. The results are shown in the following table, which showed that fogging formation was remarkably suppressed.

(mg/5 ml. of Relative Compound 5% gelatin) sensitivity Fog None 0. 18 Compound 0. 5 98 0. 16 Do 1. 0 94 0. 13 Compound 34 21.0 96 O. 11 Do 42. 0 91 0. 08

EXAMPLE 5 1- (ptolysulfonyl) -iziridine (Compound 15) or 1- phenethyl-aziridine (Compound 27) was added to a 5% gelatin solution and 5 ml. of the solution was applied on a cabinet size dry plate (about 200 sq. cm.) that had been coated with a sulfurand gold-sensitized gelatinsilver iodobromide emulsion for reversal color photographic material.

The double-coated dry plate was exposed, hardened, rinsed with water, and then developed as in Example 3, and was compared to the same photographic material treated under the same conditions without the addition of the fogging inhibitor of this invention. The results are shown in the following table, which showed the fogging formation was remarkably suppressed.

A sulfurand gold-sensitized gelatin-silver iodobromide emulsion for reversal color photographic material, to which Was added with N,N-ethylene-N'-cyclohexyl urea (Compound 3) or 2-(l-aziridinyl)-4,6-bis-ethylamino- 1,3,5-triazine (Compound 31), was applied on a film base. The sensitive film was exposed and treated as follows:

( C (min.)

1 Pie-hardening- 27 3 2- Water rinsing 27 4 3. Negative development. 27 7 4 Water rinsing 27 2 5 Reversal flash exposure 6. Color development 27 5 7 Water rinsing 27 1 8 Silver bleaching-" 27 5 9 Fixing 27 3 1O Water rinsing and dryin 9 The compositions of the above treating baths were as follows:

(1) Pre-hardening bath: same as described in Example 3. (2) Negative developing solution: same as described in The film was then bleached and fixed to remove undeveloped silver halide and reduced silver using a bleaching solution and a fixing solution having the following compositions respectively:

Example 3. Bleaching solution:

(3) ggig g lfigg 501mm 5 0 Potassium ferricyanide g 100 1". Potassium bromide g 20 N,N diethyl paraphenylene diamrne hydrochloride g 1.2 Watel 1 Sodium carbonate (monohydrate) g 20.0 Flxmg 9 Potassium bromide 03 i m thlo ulfate g 200 .1% potassium iodide Sodium sulfite (anhydrous) g 20 4 (Paratoluene sulfonamide) omego-benzoyl Acfitlc acld 45 acetamide g 1.0 Bone f "g" Caustic soda g 4.0 POtaSSlUm a um g Water to liter 1 Wat r t liter 1 (4) Silver bleaching solution:

potassium f i id g 60 After treating, the density was measured using a green Potassium bromide g 20 filter- The obtained results Were compared with those of Water to liter 1 20 a film Where a photographic material prepared under the (5) Fixi l tio same conditions but without having the fogging inhibitor Sodium thiosulfate g 100 of this invention was treated under the same conditions. Sodium sulfite g.. 15 The results are shown in the following table.

Fresh Fresh Magenta Magenta Magenta 1 Magenta 1 Quantity colored relative colored relative Compound (g. fl. mol AgX) fog sensitivity fog sens None 0. 21 100 t). 26 100 Compound 4.. 3. 52 0.16 97 0.14 103 Do..- 7. 04 0. 15 95 0. 09 97 Do... 10. 56 0. 12 93 0. 09 97 Do 14. 0s 0. 11 91 0. 07 97 Compound 28--- 8. 80 0. 16 100 l). 08 99 Do 17.60 0. 16 95 0. 09 90 Do 26. 0. 12 9s 0. 07 90 Aiter aging for 2 days at 50 C. and 80% RH.

The photographic properties of the thus obtained color From the above table it is clear that the magenta photographic film were compared with those of a film colored fog was markedly reduced while the sensitivity treated under the same conditions but containing no Was not much reduced. Moreover, it should be noticed fogging inhibitor of this invention. The results are shown 40 that the photographic material of this invention was in the following table, which show that the maximum stable after aging. density after color development was remarkably increased Almost the same results were obtained with other comcaused by the reduction of fogging in the negative depounds having a single aziridine group. velopment. What is claimed is:

1 A photographic material comprising a support, and Qua tity a silver halide photographic emulsion layer containing a Compound (s gg 25 5;; gifgg'}? stabilizing amount as a fogging inhibitor, said fogging lnhrbitor being a compound selected from the group con- NOIlG 0 NO- 1 sisting of: Compound 3 13. 0 2. 3 No. 2

Do 26.0 3.0 No.3 Compound31 7.3 2.2 No.4

Do 14.6 2.7 No.5

1 These curves are shown in the accompanying drawing. /R1

A sulfurand gold-sensitized gelatln-srlver iodobro- H R mide emulsion for a negative color photographic material C T 3 was mixed with 1-((3-sulfo-4-phenoxy)benzene)-3-heptadecyl-S-pyrazolone as a coupler by adding 20 parts by weight of an aqueous alkaline solution of the coupler (the coupler 1 g. per 2.5 ml. of 5% caustic soda) per l 100 parts by weight of the emulsion, and the mixture was OH R added to N,N-ethylene-N.-phenyl urea (Compound 4) T 3 or 2-(l-aziridinyl)-4,6-bismethoxy-1,3,5-triazine (Com- R pound 2 8). The emulsion was, after adjusting the pH to 1 7.0 with citric acid, applied on a film base. The obtained 2 C sensitive film was subjected to a conventional color development using a color developing solution having the 1] I N N HRs following composition:

C N,N-diethyl paraaminoaniline,sulfate g 2.0 Sodium sulfite g 2.0 Sodium carbonate (monohydrate) g 50.0 Hydroxylamine hydrochloride g 1.5 Potassium bromide g 1.0 wherein X represents a member selected from the class Water to ;liter consisting of -CO, CS, and SO Y represents 1 1 a member selected from the class consisting of an alkyl group, an aryl group, and

R and R each represents a member selected from the class consisting of a hydrogen atom, an alkyl group, a cyclic alkyl group, an aryl group, and an aralkyl group; R R and R each represents a member selected from the class consisting of a hydrogen atom, a methyl group, and an ethyl group; A represents a member selected from the class consisting of a hydrogen atom, C C alkyl, COOR'] (where R represents a member selected from the class consisting of an alkyl group, an aryl group, and an aralkyl group), CN, CONH COCH and an aryl group; R represents a member selected from the class consisting of a hydrogen atom, a methyl group, and CH COOR R represents an alkyl group; In and n each represents or 1; and Z and Z each represents a member selected from the class consisting of NH NH.R

and OR (where R, and R are as defined above).

2. The silver halide photographic sensitive material as claimed in claim 1 wherein the amount of said compound is about 0.1 to 100 g. per 1 mol of the silver halide in said emulsion.

3. The silver halide photographic sensitive material as claimed in claim 1 wherein said compound is one shown by the general formula wherein X represents a member selected from the class consisting of CO-, CS, and --SO Y represents a member selected from the class consisting of an alkyl group, an aryl group, and

(where R, and R each represents a member selected from the class consisting of a hydrogen atom, an alkyl group, a cyclic alkyl group, an aryl group, and an aralkyl group); and R R and R each represents a hydrogen atom, a methyl group, and an ethyl group.

4. The silver halide photographic sensitive material as claimed in claim 1 wherein said compound is one shown by the general formula H-Rs wherein A represents a member selected from the class consisting of a hydrogen atom, C C, alkyl, --COOR7 (where R represents a member selected from the class consisting of an alkyl group, an aryl group, and an aralkyl gro p), CN, CONH COCH and an aryl group; R R and R each represents a member selected from the class consisting of a hydrogen atom, a methyl group, and an ethyl group; R represents a member selected from the class consisting of a hydrogen atom, a methyl group, and CHgCOORg (where R represents an alkyl group); and m and it each represents 0 or 1.

12 5. The silver halide photographic sensitive material as claimed in claim 1 wherein said compound is one shown by the general formula wherein R R and R each represents a member selected from the class consisting of a hydrogen atom, a methyl group, and an ethyl group and Z and Z each represents a member selected from the class consisting of NH2, NH.R

and -OR (where R and R each represents a member selected from the class consisting of a hydrogen atom, an alkyl group, a cyclic alkyl group, an aryl group, and an aralkyl group).

6. A silver halide photographic sensitive material comprising a support, a silver halide photographic emulsion layer, and a protective coating layer, at least one of said layers containing a stabilizing amount of a fogging inhibitor, said fogging inhibitor being a compound selected from the group consisting of:

wherein X represents a member selected from the class consisting of CO, CS, and SO Y represents a member selected from the class consisting of an alkyl group, an aryl group, and

R and R each represents a member selected from the class consisting of a hydrogen atom, an alkyl group, a cyclic alkyl group, an aryl group, and an aralkyl group; R R and R each represents a member selected from the class consisting of a hydrogen atom, a methyl group, and an ethyl group; A represents a member selected from the class consisting of a hydrogen atom, C -C alkyl, COOR, (where R represents a member selected from the class consisting of an alkyl group, an aryl group, and an aralkyl group), CN, -CONH COCH and an aryl group; R represents a member selected from the class consisting of a hydrogen atom, a methyl group, and CH COOR R represents an alkyl group; m and n each represents 0 or 1; and Z and Z each represents a member selected from the class consisting of NH -NH.R

It. and 4=O-R., (where R, and R are as defined above).

7. The silver halide photographic sensitive material as claimed in claim 6 wherein said layer containing the compound is the silver halide photographic emulsion layer and the amount of said compound is about 0.1-100 g. per 1 mole of the silver halide in said emulsion.

8. The silver halide photographic sensitive material as claimed in claim 6 wherein said layer containing the compound is a protective coating layer and the amount of said compound 0.5 to 500 g. per 1 kg. of gelatin in said layer.

9. The silver halide photographic sensitive material as claimed in claim 1, wherein said antifoggant compound is a member selected from the group consisting of methyl- 3-( l-aZiridinyl)-propionate, 1-(2 methyl 1 aziridinyl)- propionamide, N,N-ethy1ene-N-phenyl urea, l-aziridinylpropionitrile, 1-acetyl-2-methyl-aziridine, 2-(1-azi1'idinyl)- 4,6 bis-methoxy-1,3,5-triazine, l-benzoyl-aziridine, 2-(1- aziridinyl)-4-anilin0-6-phenoxy-1,3,5 triazine, l-(p-tolyl- 14 sulfonyD-aziridine, l-phenethyl-aziridine, N,N-ethy1ene N'-cyclohexyl urea and 2 (1 aziridinyl) 4,6 bis-ethylamino-1,3,5-triazine.

10. The silver halide photographic sensitive material as claimed in claim 9, wherein said silver halide emulsion is a silver iodobromide gelatin emulsion.

References Cited UNITED STATES PATENTS 5/1961 Allen et a1. 96109X 4/1964 Corben et al 96109 US. Cl. X.R. 96107 

